Functionalized cyclopentene-derived oligomer mixtures, their preparation and their use

ABSTRACT

Functionalized cyclopentene-derived oligomer mixtures are prepared by reacting oligomer mixtures which contain ethyleneic double bonds in one or more reaction steps starting from cyclopentene-derived oligomer mixtures of the formula I 
     
       
         R 1 R 2 C═[═CH—(CH 2 ) 3 —CH═] n ═CR 3 R 4   (I) 
       
     
     where 
     n is an integer from 1 to 15, and 
     R 1 , R 2 , R 3  and R 4  are, independently of one another, hydrogen or alkyl, 
     and are used as described.

This application is a 371 of PCT/EP97/07260 filed Dec. 23, 1997.

Functionalized cyclopentene-derived oligomer mixtures, their preparationand their use

The present invention relates to functionalized cyclopentene-derivedoligomer mixtures, processes for their preparation by hydroformylationand, where appropriate, further reaction of corresponding oligomermixtures which contain ethylenic double bonds, and their use.

The processing of petroleum by steam cracking results inter alia in ahydrocarbon mixture which is called the C₅ cut and has a high totalolefin content of, for example, about 50%, of which about 15% is made upof cyclopentene and the remainder of acyclic monoolefins, especiallyn-pentene (about 15% by weight) and other isomeric pentenes (about 20%by weight). This mixture can, if required, before further processing besubjected to partial catalytic hydrogenation so that dienes areessentially no longer present then. To isolate the cyclopentane whichcomprises about 8% of the C₅ cut and which is employed, for example, aspropellent as substitute for the CFCs and HFCs which are of concern withregard to damage to the atmosphere, and where appropriate to isolate theother saturated acyclic pentanes, it is necessary in the prior art tosubject the C₅ cut to work up by distillation. This is technically avery complicated process when acyclic and cyclic C₅ olefins, inparticular cyclopentene, are simultaneously present. There is thus aneed for a process for removing cyclopentene and, where appropriate,other monoolefins from the C₅ cut other than by distillation, wherepossible with simultaneous production of a new product of value.

It is possible for this purpose to subject the C₅ cut to a metathesisreaction in the presence of a transition metal catalyst, resulting innew cyclopentene-derived oligomer mixtures with ethylenic double bonds.

A known process for the functionalization of polymers with ethylenicdouble bonds is hydroformylation. Thus, for example, M. P. McGrath etal., describe, in J. Appl. Polym. Sci. 56, (1995) 533 et seq., thehydroformylation of EPDM polymers and polybutadienes with HRhCO(PPh₃)₃or Rh(CO)₂acac (acac=acetylacetonato) as hydroformylation catalysts intoluene. Reviews on the hydroformylation of polymers with olefinicdouble bonds, such as polyisoprene or styrene/butadiene copolymers, aregiven by N. T. McManus et al. in J. Macromol. Sci., Rev. Macromol. Chem.Phys. C35(2) (1995) 239-285.

Aldehyde-functionalized polymers of this type in turn permit reactionsto be carried out on the polymer, ie. conversion into or attachment ofnew functionalities which confer new properties on the polymer.

C. Azuma et al. describe in J. Polym. Sci., Polymer Chemistry Edition,18, (1980) 781 et seq. the hydroformylation of a polypentenamer with anumber average molecular weight of 94,000 in the presence of anHRhCO(PPh₃)₃ catalyst, and the subsequent conversion into the oxoalcohols with various reducing agents such as sodium borohydride. Theamounts of catalyst needed for this hydroformylation are extremely highat about 5000 ppm. Hydroformylation of the polymer is possible only to amaximum aldehyde content of 30 mol %, otherwise insoluble productsresult. It is likewise necessary for the hydroformylated polymers to bereacted further immediately, without isolation, otherwise crosslinkingoccurs, likewise resulting in completely insoluble products.

K. Weissermel, H. J. Arpe, Industrielle Organische Chemie, 4th edition,1994, VCH Weinheim, pages 137 et seq. describe the hydroformylation (oxosynthesis) of olefins by reaction with carbon monoxide and hydrogen inthe presence of a catalyst and generally at elevated temperatures underelevated pressures. The oxo aldehydes obtained therefrom have virtuallyno importance as final products but are important reactive intermediatesfor preparing oxo alcohols, oxo carboxylic acids and aldol condensates.It is furthermore possible for oxo aldehydes to be converted byreductive amination with ammonia or a primary or secondary amine in thepresence of a reducing agent into the corresponding amines.

The oxo alcohols can in principle be prepared together with thehydroformylation, usually at elevated temperature, in a one-stagesynthesis because the hydroformylation catalysts are generally alsosuitable for further hydrogenation of the oxo aldehydes. However, theoxo aldehydes are usually first isolated and then subjected to acatalytic hydrogenation on a specific hydrogenation catalyst selectedfrom metals in group VIII or Ib, eg. a Cu or Ni catalyst.

To prepare oxo carboxylic acids, the oxo aldehydes can be oxidized withmild oxidizing agents, in the simplest case with air or with H₂O₂ in thepresence of acids. The oxidation with air can take place eithercatalytically in the presence of metal salts or else in the absence ofcatalysts at up to about 100° C. under pressures up to about 7 bar.

Houben-Weyl, Methoden der organischen Chemie, Volume XI/1, 1957, pages602 et seq., describes the reduction of condensates of ammonia or aminesand carbonyl compounds, and the reductive amination of carbonylcompounds, the latter, eg. an aldehyde, being reacted with ammonia or aprimary or secondary amine in the presence of a reducing agent withoutisolation of an intermediate. The reducing agent generally used ishydrogen in the presence of a hydrogenation catalyst, but it is alsopossible to use other reducing agents, such as formic acid and itsderivatives. None of the abovementioned publications refers to a processfor functionalizing oligomers derived from cyclopentene and obtainableby a metathesis reaction of the C₅ cut from petroleum processing.

It is an object of the present invention to provide a process forfurther processing of the new oligomer mixtures produced by a metathesisreaction on the C₅ cut.

We have found that this object is achieved by a process for preparingfunctionalized cyclopentene-derived oligomer mixtures, where thecyclopentene-derived oligomer mixtures which contain ethylenic doublebonds are subjected to a hydroformylation and, where appropriate,further functionalizations.

The invention thus relates to a process for preparing functionalizedcyclopentene-derived oligomer mixtures by a single stage or multistagefunctionalization of at least some of the ethylenic double bonds presentin an oligomer mixture of the formula I

R¹R²CCH—(CH₂)₃—CH_(n)CR³R⁴  (I)

where n is an integer from 1 to 15, and R¹, R², R³ and R⁴ are,independently of one another, hydrogen or alkyl.

The value of n in the formula I is the number of cyclopentene unitsintroduced by a ring-opening metathesis reaction into thecyclopentene-derived oligomer mixtures. The oligomer mixtures of theformula I preferably used for the process according to the invention arethose where the value of n is >1 in a proportion which is as large aspossible, eg. at least 40% by weight (determined by integration of areasin the gas chromatograms). The value of n and thus the extent of thering-opening metathesis can be influenced by the activity of themetathesis catalyst used and the ratio of acyclic to cyclic olefins.

The radicals R¹, R², R³ and R⁴ in the formula I are, independently ofone another, hydrogen or alkyl, where the term “alkyl” embracesstraight-chain and branched alkyl groups.

These are preferably straight-chain or branched C₁-C₁₅-alkyl, preferablyC₁-C₁₀-alkyl, particularly preferably C₁-C₅-alkyl, groups. Examples ofalkyl groups are, in particular, methyl, ethyl, propyl, 1-methylethyl,butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl,1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl,1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl,1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl,2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl,1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, decyl, dodecyl, etc.

The degree of branching and the number of carbon atoms in the terminalalkyl radicals R¹, R², R³ and R⁴ depend on the structure of the acyclicmonoolefins in the hydrocarbon mixture used and on the activity of thecatalyst. The activity of the catalyst also influences the extent ofcross-metathesis (self-metathesis) of the acyclic olefins to formolefins which have novel structures and into which cyclopentene is thenformally inserted in a ring-opening metathesis polymerization.

The oligomer mixtures of the formula I used according to the inventionfor the functionalization are obtainable by a metathesis reaction ofhydrocarbon mixtures comprising acyclic and cyclic olefins.

Preferably used is a hydrocarbon mixture which results from theindustrial processing of petroleum and which can, if required, besubjected beforehand to a partial catalytic hydrogenation to removedienes. A particularly suitable example is a mixture (C₅ cut) which isenriched in saturated and unsaturated C₅ hydrocarbons. The C₅ cut can beobtained, for example, by subjecting the pyrolysis gasoline produced inthe steam cracking of naphtha firstly to a selective hydrogenation, inorder to convert the dienes and acetylenes present therein selectivelyinto the corresponding alkanes and alkenes, and then to a fractionaldistillation, resulting in the C₆-C₈ cut, which is important for furtherchemical syntheses and which contains the aromatic hydrocarbons, as wellas the C₅ cut used for the process for preparing the oligomer mixturesof the formula I.

The C₅ cut generally has a total olefin content of at least 30% byweight, preferably at least 40% by weight, in particular at least 50% byweight.

Suitable C₅ hydrocarbon mixtures in this connection are those with atotal cyclopentene content of at least 5% by weight, preferably at least10% by weight, in particular at least 12% by weight, and in general notmore than 30% by weight, preferably not more than 20% by weight.

Furthermore, the proportion of pentene isomers in the acyclicmonoolefins in suitable C₅ hydrocarbon mixtures is at least 70% byweight, preferably at least 80% by weight, in particular at least 90% byweight.

Preferably used for preparing the oligomer mixtures of the formula I isa C₅ cut produced industrially with a total olefin content of, forexample, 50 to 60% by weight, such as about 56%, a cyclopentene contentof, for example, 10 to 20%, such as about 15% by weight, and a penteneisomer content of, for example, 33 to 43% by weight, such as about 38%by weight, consisting of about 16% by weight n-pentene and about 22% byweight isomeric pentenes.

It is also possible furthermore to use a hydrocarbon mixture whichcomprises the C₅ cut and a petroleum fraction containing acyclic C₄olefins (distillate 2) or the C₅ cut and ethene.

The metathesis reaction of the hydrocarbon mixture comprises

a) disproportionation of the acyclic monoolefins in the hydrocarbonmixture (C₅ cut) by cross-metathesis,

b) oligomerization of the cyclopentene by ring-opening metathesis,

c) chain termination by reaction of the oligomers from b) with anacyclic olefin in the hydrocarbon mixture or a product from a), wheresteps a) and/or b) and/or c) may take place more than once on their ownor in combination.

Step a)

Combinations of cross-metathesis of different, and self-metathesis ofidentical, acyclical olefins, and repetition of this reaction, result ina large number of monoolefins which differ in structure and number ofcarbons and which form the end groups of the oligomers of the formula I.The double bond content of the oligomers is also influenced by theproportion of cross-metathesis products, which increases with increasingactivity of the catalyst used. Thus, for example, ethene is liberated inthe self-metathesis of 1-pentene and may, where appropriate, escape asgas, which removes one double-bond equivalent from the reaction. At thesame time there is an increase in the proportion of oligomers withoutterminal double bonds.

Step b)

The average number of cyclopentene insertions into the growing chain inthe form of a ring-opening metathesis polymerization determines theaverage molecular weight of the cyclopentene oligomer mixture of theformula I which is formed. The average molecular weight of the oligomermixtures of the formula I formed by the process according to theinvention is preferably at least 274, which corresponds to an averagenumber of three cyclopentene units per oligomer.

Step c)

Chain termination takes place by reaction of an oligomer which still hasan active chain end in the form of a catalyst complex (alkylidenecomplex) with an acyclic olefin, with, in the ideal case, an activecatalyst complex being recovered. The acyclic olefin in this case may bederived unchanged from the hydrocarbon mixture originally employed forthe reaction, or have been previously modified in a cross-metathesis instage a).

Suitable catalysts for the metathesis are known and comprise homogeneousand heterogeneous catalyst systems. The catalysts suitable for preparingoligomer mixtures of the formula I are generally based on a transitionmetal of group VIb, VIIb or VIII of the Periodic Table, preferredcatalysts being based on Mo, W, Re and Ru.

Suitable homogeneous catalyst systems are generally transition metalcompounds which are able, where appropriate in combination with acocatalyst and/or where appropriate in the presence of the olefinprecursors, to form a catalytically active metal carbene complex.Systems of this type are described, for example, by R. H. Grubbs inComprehensive Organomet. Chem., Pergamon Press, New York, Volume 8, page499 et seq. (1982).

Suitable catalyst/cocatalyst systems based on W, Mo and Re may, forexample, comprise at least one soluble transition metal compound and analkylating agent. These include, for example,MOCl₂(NO)₂(PR₃)₂/Al₂(CH₃)₃Cl₃; WCl₆/BuLi; WCl₆/EtAlCl₂(Sn(CH₃)₄)/EtOH;WOCl₄/Sn(CH₃)₄; WOCl₂(O-[2,6-Br₂—C₆H₃])/Sn(CH₃)₄; CH₃ReO₃/C₂H₅AlCl₂, andthe last four mentioned are preferred for the process according to theinvention.

Further transition metal alkylidene complexes suitable as metathesiscatalysts are described by R. R. Schrock in Acc. Chem. Res., 23, (1990)158 et seq. These are generally tetracoordinate Mo- and W-alkylidenecomplexes which additionally have two bulky alkoxy and one imido ligand.Preferably used for the process according to the invention are((CH₃)₃CO)₂Mo(═N—[2,6-(i-C₃H₇)₂—C₆H₃])(═CHC(CH₃)₂C₆H₅ and[(CH₃)₂C(CH₃)O]₂Mo(═N—[2,5-(i-C₃H₇)—C₆H₃])(═CH(CH₃)₂C₆H₅).

The catalysts particularly preferably used as homogeneous metathesiscatalysts are those described in Angew. Chem. 107 (1995) 2179 et seq. inJ. Am. Chem. Soc. 118 (1996) 100 et seq., and in J. Chem. Soc., Chem.Commun., (1995) 1127 et seq. These include, in particular,RuCl₂(═CHR)(PR′₃)₂, preferably RUCl₂(═CHC₆H₅) (P(C₆H₁₁)₃)₂,(η⁶-p-cymene)RuCl₂(P(C₆H₁₁)₃)/(CH₃)₃SiCHN₂ and(η⁶-p-cymene)RuCl₂(P(C₆H₁₁l)₃/C₆H₅CHN₂. The two last-mentioned aregenerated in situ from one mol equivalent of(η⁶-p-cymene)RuCl₂(P(C₆H₁₁)₃) and 3 mol equivalents of diazoalkane((CH₃)₃SiCHN₂ or C₆H₅CHN₂).

Suitable heterogeneous catalyst systems generally comprise a transitionmetal compound on an inert carrier, which compound is able to form acatalytically active alkylidene complex without cocatalyst, by reactingwith the olefin precursors. Preferably used for this purpose are Re₂O₇and CH₃ReO₃ on Al₂O₃ as carrier material.

The abovementioned homogeneous and heterogeneous catalyst systems differgreatly in their catalytic activity, especially with regard tocross-metathesis (step a)), and influence the product distribution inthe cyclopentene-derived oligomer mixtures of the formula I. Thus, theruthenium-based homogenous catalyst systems RuCl₂(═CHC₆H₅) (P(C₆H₁₁)₃)₂,(η⁶-p-cymene)RuCl₂(P(C₆H₁₁)₃)/(CH₃)₃SiCHN₂ and(η⁶-p-cymene)RuCl₂(P(C₆H₁₁)₃)/C₆H₅CHN₂ are particularly suitable.

In this connection, the first-mentioned ruthenium complex displayshigher catalytic activity than the two last-mentioned, which, withreaction conditions which are otherwise the same, results in increasedcross-metathesis, with liberation of ethene to some extent too, and theresulting cyclopentene-derived oligomer mixture of the formula I thushaving a somewhat smaller proportion of double bonds, which ismanifested, for example, by a lower iodine value. In addition, owing tothe cross-metathesis, a larger number of acyclic olefins withoutterminal double bonds is available, so that using the first-mentionedhomogeneous ruthenium catalyst results in more cyclopentene-derivedoligomers of the formula I which have only one or no terminal doublebond. The two last-mentioned ruthenium complexes have a somewhat lowercatalytic activity than the one mentioned first, so that, using them inthe process according to the invention, results in cyclopentene-derivedoligomer mixtures of the formula I which have a higher proportion ofdouble bonds and thus a higher iodine value and a larger proportion ofterminal double bonds.

The heterogeneous catalyst systems also display the activity differencesdescribed above with the corresponding influence on the metathesisproducts. CH₃ReO₃ on Al₂O₃ as heterogeneous catalyst has a highercatalytic activity than the corresponding homogeneous catalyst systemcomposed of CH₃ReO₃/(C₂H₅)AlCl₂.

It is thus possible if desired to obtain cyclopentene-derived oligomermixtures of the formula I with varying proportions of double bonds andvarying proportions of terminal double bonds, depending on the catalystused.

The cyclopentene oligomers of the formula I obtained in the describedprocess have an iodine value of at least 250 g I₂/100 g oligomers,preferably at least 300 g I₂/100 g oligomers. The average molecularweight of the cyclopentene-derived oligomers is at least 274 g/mol,which corresponds to an average conversion of three cyclopentene unitsper oligomer, assuming chain termination by an acyclic pentene (and notby a cross-metathesis product) in this case.

a) Hydroformylation

The process according to the invention for preparing functionalizedcyclopentene-derived oligomer mixtures by reacting the previouslydescribed oligomers of the formula I which contain ethylenic doublebonds comprises initially preparing hydroformylated oligomer mixtures byreacting the oligomer mixtures of the formula I with carbon monoxide andhydrogen in the presence of a hydroformylation catalyst.

Suitable catalysts for the hydroformylation are known and generallycomprise a salt or a complex compound of an element of group VIII of thePeriodic Table. Salts, and, in particular, complex compounds of rhodiumor of cobalt are preferably used for the process according to theinvention.

Examples of suitable salts are the hydrides, halides, nitrates,sulfates, oxides, sulfides or the salts with alkyl- or arylcarboxylicacids or alkyl- or arylsulfonic acids. Examples of suitable complexcompounds are the carbonyl compounds and carbonyl hydrides of saidmetals, and complexes with amine, triarylphosphine, trialkylphosphine,tricycloalkylphosphine, olefins, or dienes as ligands. It is alsopossible to prepare catalyst systems in situ from the abovementionedsalts and said ligands.

Suitable alkyl radicals in the ligands are the above-described linear orbranched C₁-C₁₅-alkyl, in particular C₁-C₅-alkyl, radicals. Cycloalkylis preferably C₃-C₁₀-cycloalkyl, in particular cyclopentyl andcyclohexyl, which may also be substituted by C₁-C₄-alkyl groups. Aryl ispreferably phenyl (Ph) or naphthyl, which is unsubstituted orsubstituted by 1, 2, 3 or 4 C₁-C₄-alkyl, C₁-C₄-alkoxy, eg. methoxy,halogen, preferably chlorine, or hydroxyl, which may also beethoxylated.

Suitable rhodium catalysts and catalyst precursors are rhodium(II) andrhodium(III) salts such as rhodium(III) chloride, rhodium(III) nitrate,rhodium(III) sulfate, potassium rhodium sulfate (rhodium alum),rhodium(II) and rhodium(III) carboxylate, preferably rhodium(II) andrhodium(III) acetate, rhodium(III) oxide, salts of rhodium(III) acid andtrisammoniumhexachlororhodate(III).

Also suitable are rhodium complexes of the formula RhX_(m)L¹L²(L³)_(n)where X is halide, preferably chloride or bromide, alkyl- orarylcarboxylate, acetylacetonate, aryl- or alkylsulfonate, in particularphenylsulfonate and toluenesulfonate, hydride or the diphenyltriazineanion, L¹, L², L³ are, independently of one another, CO, olefins,cycloolefins, preferably cyclooctadiene (COD), dibenzophosphol,benzonitrile, PR₃ or R₂P-A-PR₂, m is 1, 2 or 3 and n is 0, 1 or 2. R(the R radicals can be identical or different) means alkyl, cycloalkyland aryl radicals, preferably phenyl, p-tolyl, m-tolyl, p-ethylphenyl,p-cumyl, p-t-butylphenyl, p-C₁-C₄-alkoxyphenyl, preferably p-anisyl,xylyl, mesityl, p-hydroxyphenyl, which may also be in ethoxylated form,isopropyl, C₁-C₄-alkoxy, cyclopentyl or cyclohexyl. A is 1,2-ethylene or1,3-propylene. L¹, L² or L³ are, independently of one another,preferably CO, COD, P(phenyl)₃, P(i-propyl)₃, P(anisyl)₃, P(OC₂H₅)₃,P(cyclohexyl)₃, dibenzophosphol or benzonitrile. X is preferablyhydride, chloride, bromide, acetate, tosylate, acetylacetonate or thediphenyltriazine anion, in particular hydride, chloride or acetate.

Particularly preferred rhodium complexes are Rh(CO)₂acac and the rhodiumcarbonyl compounds such as tetrarhodium dodecacarbonyl or hexarhodiumhexadecacarbonyl, which are used alone or together with phosphines. AnRh(CO)₂acac/P(phenyl)₃ catalyst is particularly preferably used, themolar ratio of the amounts Rh(CO)₂acac to P(phenyl)₃ being about 1:2 to1:10.

Examples of suitable cobalt compounds are cobalt(II) chloride,cobalt(II) sulfate, cobalt(II)nitrate, their amine or hydrate complexes,cobalt carboxylates, such as cobalt acetate, cobalt ethylhexanoate,cobalt naphthoate and the carbonyl complexes of cobalt such as dicobaltoctacarbonyl, tetracobalt dodecacarbonyl and hexacobalthexadecacarbonyl. Preferably used for the process according to theinvention are the cobalt carbonyl complexes and, in particular, dicobaltoctacarbonyl.

Said compounds of rhodium and cobalt are known in principle and areadequately described in the literature or they can be prepared by theskilled worker in a similar way to the compounds already known. Thispreparation may also take place in situ, in which case the catalyticallyactive species can also be formed from the abovementioned compounds ascatalyst precursors only when the hydroformylation conditions areapplied.

The hydroformylation catalyst is generally used in amounts of from 1 to150 ppm, preferably 1 to 100 ppm. The reaction temperature is generallyin the range from room temperature to 200° C., preferably 50 to 150° C.

The reaction can be carried out under a pressure of from about 10 to 650bar.

It is possible according to the invention to use as hydroformylationcatalyst a Rh(CO)₂acac/P(phenyl)₃ catalyst where the molar ratio of theamounts of Rh(CO)₂acac to P(phenyl)₃ is about 1:2 to 1:10, preferablyabout 1:3 to 1:7. Compared with hydroformylation catalysts withoutphosphine substituents, rhodium-triphenylphosphine catalysts permitreactions to be carried out at lower temperatures and under lowerpressures, with involvement preferably only of terminal double bonds.The reaction temperature with this catalyst system is about 80 to 120°C. under a pressure of about 1 to 30 bar.

The H₂:CO molar ratio of amounts is generally about 1:5 to about 5:1.

The invention furthermore relates to the hydroformylatedcyclopentadiene-derived oligomer mixtures obtained by the processaccording to the invention. The resulting hydroformylated oligomers havea carbonyl value of, preferably, at least 150 mg, in particular 250 mg,KOH/g product preferably at least 300 mg KOH/g product. It is preferredfor most of the ethylenic double bonds present in the precursor to beconverted by the hydroformylation into aldehydes or, as statedhereinafter, where appropriate also into alcohols, so that the iodinevalue of the hydroformylated oligomers is preferably ≦60 g I₂/100 goligomers.

The hydroformylated oligomers are advantageously liquid, owing to theirlower degree of polymerization, and, in contrast to the hydroformylatedpolypentenamers described in the Journal of Polymer Science, PolymerChemistry Edition 18 (1980) 781 et seq., show less of a tendency tocrosslinking. The hydroformylation products thus retain their solubilityin organic solvents.

The invention further relates to the use of the hydroformylatedcyclopentene-derived oligomer mixtures as intermediates for furtherprocessing by functionalization of at least some of the aldehydefunctionalities present therein.

The hydroformylated oligomer mixtures are furthermore suitable formodifying polymers, eq. as crosslinkers, as additives in leathertanning, and as biocides.

b) Oxo Carboxylic Acids

The invention further relates to a process for preparingcyclopentene-derived oligomer mixtures with carboxyl functionalities,where the previously described hydroformylated oligomer mixtures arereacted in the presence of an oxidizing agent.

It is generally possible to use a large number of different oxidizingagents and processes for oxidizing aldehydes to carboxylic acids, asdescribed, for example, in J. March, Advanced Organic Chemistry,published by John Wiley & Sons, 4th Edition, page 701 et seq. (1992).Examples include oxidation with permanganate, chromate, etc. In apreferred embodiment of the process according to the invention,atmospheric oxygen is used to oxidize the hydroformylatedcyclopentene-derived oligomer mixtures. Oxidation with air can takeplace either catalytically in the presence of metal salts or else in theabsence of catalysts. The metals preferably employed are those able tochange valency, such as Cu, Fe, Co, Mn etc. Preferably no catalyst isused in the process according to the invention. Oxidation withatmospheric oxygen can take place in a neutral or acidic medium andpreferably takes place in the process according to the invention in analkaline medium with addition of a base such as NaOH, KOH etc. It iseasily possible in atmospheric oxidation to control the conversion bythe reaction time. The oligomer mixtures with carboxyl functionalitiespreferably obtained on use of an oxygen-containing gas as oxidizingagent have an acid value of at least 50 mg KOH/g product, preferably atleast 70 mg KOH/g product.

In another preferred embodiment of the process according to theinvention, an aqueous hydrogen peroxide solution is used in combinationwith a carboxylic acid, preferably acetic acid, as oxidizing agent. Thisresults in oligomer mixtures with carboxyl functionalities with the acidvalue being at least 150 mg KOH/g product, preferably at least 200 mgKOH/g product.

The invention further relates to cyclopentene-derived oligomer mixtureswith carboxyl functionalities which can be obtained by the processesdescribed above. Their acid value is, as described above, at least 50 mgKOH/g product, but preferably at least 70 mg KOH/g product, depending onthe reaction procedure.

The invention further relates to the use of the oligomer mixtures withcarboxyl functionalities, which may also be esterified, in particularwith C₁-C₁₈ alkanols, for preparing copolymers, as complexing agents,eg. as incrustation inhibitors, as surfactant component, as concreteplasticizer and for sea water desalination.

c) Oxo Alcohols

The invention further relates to a process for preparingcyclopentene-derived oligomer mixtures with hydroxyl functionalities,where the hydroformylated oligomer mixtures from stage a) are reactedwith hydrogen in the presence of a hydrogenation catalyst.

Suitable hydrogenation catalysts are generally transition metals such asCr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru etc., or mixtures thereof, whichmay be applied, to increase the activity and stability, to carriers suchas active carbon, alumina, kieselguhr etc. To increase the catalyticactivity, Fe, Co and, preferably, Ni can also be used in the form of theRaney catalysts as metal sponge with a very large surface area.

Preferably used as catalyst for the process according to the inventionfor preparing oligomer mixtures with hydroxyl functionalities is Raneynickel.

The hydrogenation of the oxo aldehydes from stage a) preferably takesplace at elevated temperatures under elevated pressure, depending on theactivity of the catalyst. When Raney nickel is used as catalyst, thereaction is carried out at about 80 to 150° C. under a pressure of about50 to 350 bar.

In a particular embodiment of the process according to the invention,the preparation of the oligomer mixtures with hydroxyl functionalitiestakes place together with the hydroformylation in a one-stage reaction.This is done by reacting the cyclopentene-derived oligomer mixtures withethylenic double bonds of the formula I with carbon monoxide andhydrogen in the presence of a hydroformylation catalyst which is alsosuitable for the further hydrogenation to give the oxo alcohols. Inprinciple, all hydroformylation catalysts are also suitable forcatalytic hydrogenations, but generally higher temperatures and/orhigher pressures and/or longer reaction times, and a larger amount ofcatalysts, depending on the catalytic activity, are used than forhydroformylation on its own.

All the catalysts described in stage a) are suitable for the processaccording to the invention for hydroformylation with simultaneoushydrogenation. A cobalt carbonyl catalyst is preferably used, inparticular Co₂(CO)₈. The reaction is generally, carried out at from 100to 220° C., preferably 150 to 200° C., under a pressure of from 50 to650 bar, preferably 100 to 600 bar.

Other processes can also be used to reduce the oxo aldehydes to thealcohols. These include, for example, reduction with complex hydridessuch as LiAlH₄ and NaBH₄, reduction with sodium in ethanol by theBouveault-Blanc method, and other known processes.

The invention further relates to the cyclopentene-derived oligomermixtures with hydroxyl functionalities obtained by one of the twoprocesses described above. Conversion is preferably as complete aspossible, ie. reduction is as complete as possible so that the carbonylvalue of the oxo alcohols obtained by the process according to theinvention is small by comparison with the carbonyl value of theoligomeric oxo aldehydes employed as precursor. The maximum carbonylvalue of the oxo alcohols is generally 20. The alcohol value is at least150 mg KOH/g product, in particular 250 mg KOH/g product, preferably atleast 300 mg KOH/g product.

The invention further relates to the use of the cyclopentene-derivedoligomer mixtures according to the invention with hydroxylfunctionalities, where appropriate after alkoxylation (etherification)or esterification thereof, in particular with a C₁-C₁₈ carboxylic acid,as plasticizer, reactive thinner, antifoam, adhesive additive and aspolyol component for preparing polyurethanes.

d) Amine Synthesis

Hydrogenation of aldehydes and ketones in the presence of ammonia,primary or secondary amines results, through reductive amination, in thecorresponding primary, secondary or tertiary amines, and intramolecularcrosslinking with amino groups already converted. The invention thusrelates further to a process for preparing cyclopentene-derived oligomermixtures with amino functionalities, where the hydroformylated oligomermixtures from stage a) or the oligomer mixtures with hydroxylfunctionalities from stage c) are reacted with ammonia, a primary orsecondary amine in the presence of an amination catalyst and ofhydrogen.

The hydroformylated oligomer mixtures are preferably reacted withammonia in the presence of hydrogen and a hydrogenation catalyst,resulting in oligomer mixtures with primary amino functionalities.

The preparation of amines from aldehydes or ketones can generally becarried out as a one-stage or two-stage process. In the two-stagevariant, firstly a condensate is formed from ammonia, primary orsecondary amines on the one hand and aldehydes on the other hand in afirst reaction step, and is then hydrogenated in a second reaction step.

In a suitable embodiment of the two-stage process, the hydroformylatedoligomer mixtures from stage a) are reacted with ammonia or amines ofthe formula R-NH₂ where R is NH₂, C₁-C₁₀-alkyl, C₆-C₂₀-aryl,C₇-C₂₀-arylalkyl, C₇-C₂₀-alkylaryl or an organosilicon residue having 3to 30 carbon atoms, or with a reagent which liberates ammonia or amines,and subsequently hydrogenated.

Examples of suitable R radicals in the amines R-NH₂ are NH₂, the alkylradicals mentioned above for the oligomers of the formula I, phenyl,naphthyl, p-tolyl, o-tolyl, xylyl and tri(C₁-C₁₀)alkyl-silyl such astrimethylsilyl, tert-butyldimethylsilyl or else triarylsilyl, forexample triphenylsilyl, tri-p-tolylsilyl or trinaphthylsilyl.

Suitable reagents which liberate ammonia are in general all ammoniumsalts, preferably ammonium carbonate. Ammonium carbonate and, inparticular, ammonia are preferably used for the two-stage processaccording to the invention.

The process according to the invention for preparing oligomer mixtureswith amino functionalities is preferably carried out as one-stageprocess, in which case the hydroformylated oligomer mixtures from stagea) are reacted with ammonia, a primary or secondary amine in thepresence of an amination catalyst and of hydrogen.

The hydroformylated oligomer mixtures are preferably reacted withammonia in the presence of hydrogen and of an amination catalyst.Suitable amination catalysts for the one-stage and the two-stage processare the hydrogenation catalysts described above in stage c), preferablycopper, cobalt or nickel in the form of the Raney metals or on acarrier, and platinum.

Particularly suitable amination catalysts are the catalysts described inEP-A 394 842 and in DE-A 4 429 547 for hydrogenation of unsaturatedcompounds, which are incorporated herein by reference. This catalysthas, in the non-reduced oxide form, a content of from 20 to 75% byweight of nickel oxide, 10 to 75% by weight of zirconium dioxide and 5to 50% by weight of copper oxide, with or without up to 5% by weight ofmolybdenum oxide and with or without up to 10% by weight of manganeseoxide. Before being used according to the invention, the catalyst issubjected to a reductive treatment with hydrogen at from 180 to 300° C.for from 5 to 30 hours under a hydrogen pressure of from 1 to 300 bar.The hydrogenation catalyst particularly used for the process accordingto the invention comprises 51% by weight NiO, 17% by weight CuO, 31% byweight ZrO₂ and 1% by weight MoO₃, based on the non-reduced oxidecatalyst.

The reductive amination using the catalyst described above is carriedout at from about 100 to 250° C., preferably 150 to 230° C., under apressure of from about 100 to 300 bar, preferably from 150 to 250 bar.

It is possible if desired also to use other reduction processes toprepare the cyclopentene-derived oligomer mixtures according to theinvention with amino functionalities from the oxo aldehydes of stage a).These include, for example, reductive amination of aldehydes in thepresence of formic acid by the Leuckart-Wallach method, and otherprocesses known to the skilled worker.

The invention further relates to the cyclopentene-derived oligomermixtures with amino functionalities obtained by the process according tothe invention. Conversion in the reductive amination in stage d) ispreferably as complete as possible so that the resulting products have asmall carbonyl value of, preferably, less than 20. The side reactionwith formation of alcohols due to the oxo aldehydes undergoing reductionexclusively is of only minor importance in the process according to theinvention so that products with an alcohol value of less than 40 mgKOH/g product are obtained. The amine value is at least 150 mg KOH/gproduct, preferably at least 200 mg KOH/g product. The tertiary aminecontent is moreover low with an amine value not exceeding 20 mg KOH/gproduct.

The invention further relates to the use of the cyclopentene-derivedoligomer mixtures with amino functionalities according to the inventionas component in epoxy resins, polyamides, polyurethanes, polyureas, asdispersant, dye transfer inhibitor, paper auxiliary, soil remover,component in skin creams and hair-care compositions, crosslinker foradhesives, stabilizer for polyoxymethylene, corrosion inhibitors,textile assistants, auxiliaries for dispersions, adhesives, protectivecolloids, adhesive coatings, epoxy hardeners in aqueous dispersions,auxiliaries for dishwashing compositions, paper auxiliaries, levelingagents for textiles, solubilizers for cosmetics, for metal extraction,comlexing agents, fuel additive, lubricants, corrosion inhibitor foraqueous systems, addition to glue and resin raw materials, dye fixationon textiles, paper fixation, retention, complexing agent for metalrecycling, stabilizer for hydroxylamine, surfactants.

The invention is illustrated by means of the following non-restrictiveexamples.

EXAMPLE

The gas chromatograms were recorded using a Hewlett Packard 5890 gaschromatograph with a DB 5.30 m×0.32 mm glass capillary column and aflame ionization detector with attached integration unit.

The iodine value is defined as g iodine/100 g product and was measuredby the Kaufmann method in which about 0.2 g of test substance areweighed accurately into a 300 ml Erlenmeyer flask and dissolved in 20 mlof chloroform and, after addition of exactly 20.00 ml of brominesolution, left to stand in the dark for 2 hours. Then 10 ml of potassiumiodide solution and about 2 g of potassium iodate are added. The iodinewhich separates out is titrated against standard sodium thiosulfatesolution using starch solution as indicator until the blue colordisappears. To prepare the bromine solution used in the Kaufmann method,120 g of sodium bromide are dissolved in about 900 ml of methanol. 6.5ml of bromine are added to this, and the volume is made up to 1000 mlwith methanol. The solution is then about 0.25 molar and is stored inbrown glass bottles.

The carbonyl value is defined as mg KOH/g product. For thedetermination, about 1.5 g of test substance are weighed accurately and10 ml of toluene, 50 ml of hydroxylammonium chloride solution and 5 mlof 0.5 N HCl are added. The solution is stirred at room temperature for24 hours and titrated potentiometrically against standard sodiumhydroxide solution to the turning point. The hydroxylammonium chloridesolution is prepared by dissolving 70 g of hydroxylammonium chloride in320 ml of water, making up to 2 l with ethanol and adjusting to pH 2.5with HCl.

The acid value is defined as mg KOH/g product and was determined by theDIN 53402 method or the method in the Deutsche Arzneibuch 10 V. 3.4.1.(1993).

The alcohol value is defined as mg KOH/g product. For the determination,about 1 g of test substance is weighed accurately and, after addition of9.8 ml of acetylating reagent, left to stand at room temperature for 24hours. Then 25 ml of distilled water are added and the mixture isstirred for 15 min, 25 ml of isopropanol are added and the mixture istitrated potentiometrically against standard sodium hydroxide solutionto the turning point. The acetylating reagent is prepared by mixing 810ml of pyridine, 100 ml of acetic anhydride and 9 ml of acetic acid.

The amine value is defined as mg KOH/g product. For the determination,about 1.0 g of test substance is weighed accurately, dissolved in 50 mlof acetic acid and titrated potentiographically against 0.1 molarstandard trifluoromethane-sulfonic acid solution in acetic acid. Themethod is described in Huber, Titrationen in nichtwäBrigenLösungsmitteln, Akademisch Verlagsgesellschaft, Frankfurt a. M. page 130et seq. (1964) and in Gyenes, Titrationen in nichtwäBrigen Medien,Ferdinand Enke Verlag, Stuttgart, page 488 et seq. (1970).

The tertiary amine value is defined as mg KOH/g product. For thedetermination, about 1.0 g of test substance is weighed accurately anddissolved in ml of acetic acid and, after addition of 30 ml of aceticanhydride, heated on a water bath at 70° C. for 2 hours. After coolingto room temperature, the solution is titrated potentiographicallyagainst 0.1 molar standard trifluoromethanesulfonic acid solution inacetic acid. The method is described in Huber, Titrationen innichtwäBrigen Lösungsmitteln, Akademische Verlagsgesellschaft, Frankfurta. M., page 147 et seq. (1964) and in Gyenes, Titrationen innichtwäBrigen Medien, Ferdinand Enke Verlag, Stuttgart, page 574 et seq.(1970).

I. Preparation of Cyclopentene-derived Oligomer Mixtures of the FormulaI

Example 1

A 1:1 mixture of 17.1 mol each of cyclopentene and 1-pentene was mixedat room temperature under atmospheric pressure with a catalyst mixturegenerated in situ from 8.6 mmol of (p-cymene)RuCl₂(PCy₃) and 2 ml ofMe₃SiCHN₂ in 50 ml of CH₂Cl₂.

Slight evolution of gas was observed during this. After stirring for 3hours, the solution was chromatographed on neutral Al₂O₃, and thecolorless filtrate was distilled to remove unreacted low boilers. Theremaining colorless, low-viscosity liquid weighed 956 g and had thefollowing composition (GC percent areas): 26% C₁₀H₁₈, 22% C₁₅H₂₆, 17%C₂₀H₃₄, 13% C₂₅H₄₂, 10% C₃₀H₅₀, 7% C₃₅H₅₈, 5% C₄₀H₆₆.

Iodine value: 351 g I₂/100 g

Example 2

1 l of C₅ cut (cyclopentene content: 15%) was reacted at roomtemperature under atmospheric pressure with a solution of 0.6 mmol ofRuCl₂(═CHPh)(PCy₃)₂ in 20 ml of CH₂Cl₂. Slight evolution of gas wasobserved during this. After stirring for 1 h, the solution waschromatographed on Al₂O₃, and the colorless filtrate was distilled toremove unreacted low boilers. 96 g of a colorless, low-viscosity liquidof the following composition (GC percent areas) were obtained:

4% C₇H₁₂, 11% C₈H₁₆, 14% C₁₀H₁₈, 3% C₁₂H₂₀, 8% C₁₃H₂₄, 12% C₁₅H₂₆, 2%C₁₇H₂₈, 5% C₁₈H₃₂, 9% C₂₀H₃₄, 1% C₂₂H₃₆, 4% C₂₃H₄₀, 7% C₂₅H₄₂, 3%C₂₈H₄₈, 6% C₃₀H₅₀, 1% C₃₃H₅₆, 4% C₃₅H₅₈, 3% C₄₀H₅₈, 3% C₄₀H₆₆, 2%C₄₀H₆₆, 1% C₄₀H₆₆.

Iodine value: 329 g I₂/100 g

Example 3

A 1:1 mixture of cyclopentene and 1-pentene was pumped continuously intoa tubular reactor charged with Re₂O₇/Al₂O₃ at 60° C. under 5 bar andwith residence times of 1-3 h. The reaction product was then separatedinto a low-boiling fraction and a high-boiling fraction in a fallingfilm evaporator operated at 115° C. under atmospheric pressure, and theformer was returned to the metathesis process. The high-boiling fractionwas freed of residues of low boilers under reduced pressure. Withspace-time yields of 50-500 g l⁻¹ h⁻¹, pale yellow liquids were obtainedand were finally chromatographed on Al₂O₃. A sample had the followingcomposition (GC percent areas):

3% C₇H₁₂, 9% C₈H₁₆, 16% C₁₀H₁₈, 2% C₁₂H₂₀, 8% C₁₃H₂₄, 13% C₁₅H₂₆, 2%C₁₇H₂₈, 6% C₁₈H₃₂, 11% C₂₀H₃₄, 1% C₂₂H₃₆, 4% C₂₃H₄₀, 9% C₂₅H₄₂, 2%C₂₈H₄₈, 6% C₃₀H₅₀, 3% C₃₅H₅₈, 2% C₄₀H₆₆, 1% C₄₀H₆₆, 1% C₄₅H₇₄.

Iodine value: 349 g I₂/100 g

Example 4

1 l of C₅ cut was pumped continuously into a tubular reactor chargedwith Re₂O₇/Al₂O₃ at 60° C. under 5 bar and with residence times of 1-3h. The reaction product was separated into a low-boiling fraction and ahigh-boiling fraction in a falling film evaporator operated at 115° C.under atmospheric pressure. The latter fraction was distilled underreduced pressure to remove residues of low boilers. With space-timeyields of 20-100 g l⁻¹ h⁻¹ and cyclopentene conversions up to 70%, paleyellowish liquids were obtained and were finally chromatographed onAl₂O₃. A sample had the following composition (GC percent areas):

4% C₇H₁₂, 11% C₈H₁₆, 14% C₁₀H₁₈, 3% C₁₂H₂₀, 8% C₁₃H₂₄, 12% C₁₅H₂₆, 2%C₁₇H₂₈, 5% C₁₈H₃₂, 9% C₂₀H₃₄, 1% C₂₂H₃₆, 4% C₂₃H₄₀, 7% C₂₅H₄₂, 3%C₂₈H₄₈, 6% C₃₀H₅₀, 1% C₃₃H₅₆, 4% C₃₅H₅₈, 3% C₄₀H₆₆, 2% C₄₅H₇₄, 1%C₅₀H₈₂.

Iodine value: 325 g I₂/100 g

II. Hydroformylation (Rhodium-catalyzed)

Examples 5-9

1000 g of an oligomer from one of Examples 1-3 and a catalyst, with orwithout solvent as shown in Table 1, were introduced into a 2000 mlautoclave. The autoclave was heated to the temperature stated in Table1, increasing the pressure to the value stated in Table 1 by passing ina carbon monoxide/hydrogen mixture (molar ratio 1:1). The pressure inthe autoclave fell due to reaction of part of the gas mixture and wasmaintained by passing in further hydrogen/carbon monoxide mixture untilthe pressure was constant for 3 hours. After the required reaction time,the heating and gas introduction were switched off and the cooledautoclave was emptied through a rising tube into a storage vessel.

The degree of hydroformylation is characterized by the analyticalresults (carbonyl value, iodine value) indicated in Table 1.

TABLE 1 Rhodium-catalyzed hydroformylation Precursor Catalyst; amount ofProduct Product Example Oligomer iodine metal relative to Pressure Temp.carbonyl iodine No. from Example value oligomer (bar) (° C.) Solventvalue value 5 1 351 Rh(CO)₂acac; 5 ppm 600 130 — 430 37 6 1 351Rh(CO)₂acac; 10 ppm 600 130 — 495 <1 7 2 329 Rh(CO)₂acac; 20 ppm 280 130— 307 51 8 3 349 Rh(CO)₂acac; 100 ppm 280 130 50% 349  3 toluene 9 1 351Rh(CO)₂acac  20 100 —  15 (100 ppm)/TPP¹⁾ Molar ratio TPP/Rh = 5:1 ¹⁾TPP= triphenylphosphine

Examples 5 and 6 under 600 bar show by comparison with Examples 7 and 8under 280 bar a high selectivity for the conversion of C═C double bondsinto the corresponding aldehyde compounds. Under 280 bar there is ahigher proportion of hydrogenation and not hydroformylation.

III. Oxo Carboxylic Acid Synthesis

Example 10

Oxidation with Atmospheric Oxygen

1200 g of the hydroformylated oligomer from Example 8 were introducedwith 1200 g of toluene into a heatable vessel with a volume of 3 1. Then2.5 g of potassium hydroxide were added. The temperature was raised to40° C. and then introduction of air was started, and samples were takenat intervals. The conversion or the result of oxidation was measured bydetermining the acid value. The reaction was stopped after 120 hours.The results of the oxidation are shown in Table 2.

TABLE 2 Oxidation of the hydroformylated oligomer from Example 8 ProductExample No. Time (h) acid value 10 24 70 48 154 120 179

Example 11

Oxidation with Hydrogen Peroxide/glacial Acetic Acid

100 g of hydroformylated oligomer from Example 7 were introduced into aflask and cooled to 5° C. in an icebath. A mixture of 100 ml of 30%strength aqueous acetic acid and 100 ml of 30% strength aqueous hydrogenperoxide solution was added dropwise over the course of 7 hours,followed by stirring for one hour. The product was separated from theaqueous phase in a separating funnel, and the organic phase was washedthree times with water until neutral and then dried over sodium sulfate.The result of oxidation was measured by determining the acid value. Itwas 214 mg of KOH/g.

IV. Oxo Alcohol Synthesis

Example 12

Hydroformylation (Cobalt-catalyzed) at Elevated Temperature

1000 g of the oligomer from Example 4 were introduced with 0.13% byweight of CO₂(CO)₈, based on the oligomer, into a 2000 ml autoclave. Theautoclave was heated to 185° C. while the pressure was raised to 280 barby passing in a carbon monoxide/hydrogen mixture (molar ratio 1:1). Thepressure in the autoclave fell due to reaction of part of the gasmixture and was maintained by passing in further hydrogen/carbonmonoxide mixture until the pressure was constant for 3 hours. After 10.5hours, the heating and the gas introduction were switched off and thecooled autoclave was emptied through a rising tube into a storagevessel.

The discharge was stirred with 500 ml of 10% strength aqueous aceticacid at 100° C. while passing in air for 30 min. Two phases resulted,the lower one being the cobalt-containing water/acetic acid mixture. Thelatter was separated off. The organic phase was washed twice with 500 mlof water each time and dried. The degree of hydroformylation and thedegree of reduction were determined from the analytical results(carbonyl value, alcohol value), which are shown in Table 3.

TABLE 3 Result of the cobalt-catalyzed hydroformylation PrecursorCatalyst; amount of Product Product Product Example Oligomer iodinemetal relative to Pressure Temp. carbonyl iodine alcohol No. fromExample value oligomer (bar) (° C.) value value value 12 4 325 Co₂(CO)₈;0.13% 280 130 8 3 285

Example 13

2800 g of a hydroformylated oligomer from Example 5 were introduced with50 g of Raney nickel into a 5 l stirred autoclave. The pressure was thenadjusted with hydrogen to 280 bar and the temperature was adjusted to125° C. The pressure in the autoclave fell due to reaction of part ofthe gas and was maintained by passing in further hydrogen until (10 h)the pressure was constant for 3 hours. The heating and the gasintroduction were then switched off and the cooled autoclave was emptiedinto a storage vessel. The discharge was filtered to remove Raneynickel.

The result of hydrogenation was determined from the analytical e results(carbonyl value, alcohol value) which are shown in Table 4.

TABLE 4 Hydrogenation of an oxo aldehyde Hydroformylated PrecursorProduct Product Example oligomer from carbonyl carbonyl alcohol No.Example No. value value value 13 5 430 7 347

V. Amine Synthesis

Activation of the amination catalyst (disclosed in EP-A-194 842: 51% byweight NiO, 17% by weight CuO, 31% by weight ZrO₂, 1% by weight MoO₃):

The previously reduced and passivated catalyst (pellets) was introducedinto an autoclave, which was tested for leaks under a pressure of 20 barfor hydrogen and was then heated to 200° C., a pressure of about 30 to39 being set up. This was increased to 100 bar with hydrogen, and thecatalyst was activated at 200° C. for 16 h, followed by cooling anddecompression. The pressure vessel was evacuated and the precursor,where appropriate in a suitable solvent, eg. THF, was sucked in withexclusion of air, and nitrogen was admitted.

General method for the amination/reductive amination

After activation of the catalyst as described above, the precursor(hydroformylated oligomer from Example 7) was transferred into theevacuated autoclave, nitrogen was admitted, the amount of ammoniaindicated in Table 5 and 30 bar of hydrogen were injected, the mixturewas heated to the final temperature indicated, hydrogen was injected tothe final pressure indicated, and the reaction was carried out for theindicated time. This was followed by cooling, decompression and removalof the contents of the autoclave using a suitable solvent, eg. THF.

Example 14

15 ml of the catalyst were reduced in a stirred autoclave (300 ml) withcatalyst basket at 200° C. and 100 bar for 16 h as described above, theautoclave was charged with 50 g of 30% strength solution ofhydroformylated cyclopentene oligomer from Example 7 in THF, andreaction was carried out with 73 ml of NH₃ at 185° C. and 200 bar for 20h as described above. Removal was carried out as described with THF.

After removal of the THF in a rotary evaporator, 18.3 g of a colorlessliquid product were obtained. The reaction conditions and analyticalresults are shown in Table 5.

Example 15

15 ml of the catalyst were reduced in a stirred autoclave (300 ml) withcatalyst basket at 200° C. and 100 bar for 16 h as described above, theautoclave was charged with 60 ml of 50% strength solution ofhydroformylated cyclopentene oligomer from Experiment 8 in THF, andreaction was carried out with 50 ml of NH₃ at 200° C. and 220 bar for 20h as described above. Removal was carried out as described with THF.

After removal of the THF in a rotary evaporator, 20.3 g of a colorlessliquid product were obtained. The reaction conditions and analyticalresults are shown in Table 5.

Example 16

150 ml of the catalyst were reduced in a 2.5 l stirred autoclave withcatalyst basket at 200° C. and 100 bar for 16 h as described above, theautoclave was charged with 600 ml of 50% strength solution ofhydroformylated cyclopentene oligomer from Experiment 8 in THF, andreaction was carried out with 500 ml of NH₃ at 200° C. and 220 bar for20 h as described above. Removal was carried out with THF and, afterremoval of the solid constituents by filtration and removal of the THFin a rotary evaporator to a volume of about 500 ml, the residue wasmixed with 300 ml of toluene and evaporated in a rotary evaporator.

314 g of a colorless liquid product were obtained. The reactionconditions and analytical results are shown in Table 5.

TABLE 5 Amination tert. Precursor: Pres- A- A- Ex. NH₃ stoi- Temp. sureTime OH CO mine mine No. chiometry [° C.] [bar] [h] value value valuevalue Pre- 27 307 0 0 cursor from Ex. 7 14 1:25 185 200 20 33  3 252.7 715 1:10 200 220 20 <1  <1 231.5 9.9 16 1:10 200 220 48 15 264 12.4

We claim:
 1. A process for preparing functionalized cyclopentene-derivedoligomer mixtures by a single stage or multistage functionalization ofat least some of the ethylenic double bonds present in an oligomermixture of the formula I R¹R²CCH—(CH₂)₃—CH_(n)CH³R⁴  (I) where n is aninteger from 1 to 15, and R¹, R², R³ and R⁴ are, independently of oneanother, hydrogen or alkyl, wherein the oligomer mixtures of the formulaI are obtained by a metathesis reaction of a hydrocarbon mixturecomprising acyclic and cyclic olefins, and wherein said hydrocarbonmixture is a C₅-hydrocarbon mixture with a total cyclopentene content ofat least 5% by weight and a proportion of pentene isomers in the acyclicmonoolefins of at least 70% by weight, and wherein the oligomer mixturesof formula I are subjected to a hydroformylation to obtain ahydroformylated oligomer mixture and, optionally, furtherfunctionalization selected from: reaction in the presence of anoxidizing agent to obtain an oligomer mixture with carboxylfunctionalities, reaction with hydrogen in the presence of ahydrogenation catalyst to obtain an oligomer mixture with hydroxylfunctionalities, reaction with ammonia, or a primary or secondary aminein the presence of an amination catalyst and of hydrogen to obtain anoligomer mixture with amino functionalities.
 2. A process as defined inclaim 1, wherein the oligomer mixture of the formula I ishydroformylated with carbon monoxide and hydrogen in the presence of ahydroformylation catalyst.
 3. A hydroformylated cyclopentene-derivedoligomer mixture obtained by a process as defined in claim
 2. 4. Acyclopentene-derived oligomer mixture with carboxyl functionalitiesobtained by a process as claimed in claim
 1. 5. A process as defined inclaim 1 for preparing cyclopentene-derived oligomer mixtures withhydroxyl functionalities, wherein the hydroformylated oligomer mixtureis reacted with hydrogen in the presence of a hydrogenation catalyst. 6.The process as defined in claim 5, wherein said hydrogenation catalystis a metal of group VIII or IB of the Periodic Table of the Elements. 7.A cyclopentene-derived oligomer mixture with hydroxyl functionalities,obtained by a process as defined in claim
 1. 8. A cyclopentene-derivedoligomer mixture with amino functionalities obtained by a process asdefined in claim
 1. 9. A process as claimed in claim 1, wherein thecyclopentene-derived oligomer mixture with carboxy functionalities isesterified with a C₁-C₁₈-alkanol.
 10. An ester of a cyclopentene-derivedoligomer mixture with carboxyl functionalities with a C₁-C₁₈-alkanolobtained by a process as claimed in claim
 9. 11. A process as claimed inclaim 1, wherein the cyclopentene-derived oligomer mixture with hydroxylfunctionalities is etherified to yield an C₁-C₁₈-alkyl ether thereof.12. A C₁-C₁₈-alkyl ether of a cyclopentene-derived oligomer mixture withhydroxyl functionalities obtained by a process as claimed in claim 11.13. A process as claimed in claim 1, wherein the cyclopentene-derivedoligomer mixture with hydroxyl functionalities is esterified with aC₁-C₁₈-carboxylic acid.
 14. An ester of a cyclopentene-derived oligomermixture with hydroxyl functionalities with a C₁-C₁₈-carboxylic acidobtainable by a process as claimed in claim
 13. 15. A process forpreparing functionalized cyclopentene-derived oligomer mixtures withhydroxyl functionalities by a single stage functionalization of at leastsome of the ethylenic double bonds present in an oligomer mixture of theformula I R¹R²CCH—(CH₂)₃—CH_(n)CH³R⁴  (I) where n is an integer from 1to 15, and R¹, R², R³ and R⁴ are, independently of one another, hydrogenor alkyl, wherein the oligomer mixtures of the formula I are obtained bya metathesis reaction of a hydrocarbon mixture comprising acyclic andcyclic olefins, and wherein said hydrocarbon mixture is a C₅-hydrocarbonmixture with a total cyclopentene content of at least 5% by weight and aproportion of pentene isomers in the acyclic monoolefins of at least 70%by weight, and wherein the oligomer mixtures of formula I are subjectedto a hydroformylation at elevated temperature and under elevatedpressure.
 16. A process as claimed in claim 15, wherein the reaction iscarried out in the presence of a hydroformylation cocatalyst.
 17. Theprocess as defined in claim 15, wherein said hydrogenation catalyst isCu or Ni.